Controlled Conversion of Minerals to Pigmenting Elements Systems and Methods

ABSTRACT

The present invention may provide talc calciner systems and methods to produce better and more efficient products by engineering a* and b* values for calcinated products perhaps by processing low iron talc in an indirectly heated, multiple zoned calciner which may progressively heat the feed supply at perhaps specifics residence times to produce a desired product.

PRIORITY CLAIM

This application is a continuation of U.S. patent application Ser. No.14/259,137, filed Apr. 22, 2014, which claims priority to, and thebenefit of U.S. Patent App. No. 61/854,396 filed Apr. 22, 2013, eachapplication is hereby incorporated by reference herein in theirentirety.

BACKGROUND

The present invention relates to the field of calcining of minerals suchas talc, kaolin, and the like. In particular it relates to processes,substances, and apparatus that can enhance and achieve production of aproduct in a manner that achieves enhanced results for the product andthe end uses of the product, such as predictably and repeatablegenerating a specific L*a*b* value or perhaps otherwise afford technicalor economic advantages.

Numerous industries which produce plastics of various types, paints formultiple uses, elastomerics for roof and other coatings, paper, caulkingand other products use minerals which serve as fillers, extenders andopacifiers, and which perform functions with the base materials whichcannot occur without such fillers, extenders or opacifiers.

One such mineral is talc. Talc is commonly called hydrous magnesiumsilicate or magnesium silicate hydroxide, with the chemical formulaMg₃(Si₄O₁₀)(OH)₂. Silicon oxide tetrahedra are composed of three oxygenmolecules which form the base of tetrahedron located at the surface of asheet. The fourth oxygen molecule in the lower plane forms the opposingapex, with a silicon being located within the tetrahedron. Theseinternal sheets are bonded together by Van Der Waals forces. Sometetrahedra are reversed and have an active apex located at the surfaceof the sheet, this apex consisting of a hydroxyl group (OH) bonded tothe silicon of the tetrahedron to form a silanol group SiOH. The surfacesheets are connected together to the same internal sheets by Van DerWaals forces.

Upon heating, perhaps beginning at approximately 100° C., talc (herecommonly termed a “feed”) may undergo a series of significant changes inthe chemical nature and crystalline structure. At about 100° C., freemoisture may be evolved from talc. Then, as further heating occurs,various organic compounds may be released and the carbonate impuritiesassociated with talc may be driven off perhaps beginning at about 550°C. Additional heating may cause the crystalline water to evolve at about950° C. Heating beyond 1000° C. (commonly called hard calcination) maybe practiced to ensure conversion of the talc material to secondary,distinct materials, commonly referred to as “products” such as enstatite(MgSiO₂), protoenstatite (MgSiO₂), clinoenstatite (MgSiO₃), or the like.In the presence of some impurity materials, diopside (CaMg(SiO₃)₂) maybe formed. Such impure materials may cause formation of products such asdiopside, dolomite (calcium magnesium carbonate), chlorite (hydratedmagnesium aluminum silicate), limestone (calcium carbonate), or thelike.

Calcining of talc has been regarded as a simple process, but discoveriesdisclosed herein have shown how new and remarkable results and productsmay be achieved, including but not limited to, use of low value talcthat can be transformed into a higher value material. Past technologieshave formed ceramic pigments from talc and have created hydrophyllicsubstances. Past talc calcinations patents may have generally focused onreaching a single temperature within a calciner, and other temperaturemeasurements are taken as resultant of the firing temperature. Otherpast technologies have used direct-fired calcination in rotary kilns,which may feature a flame at the discharge end, with the hot combustiongases moving toward the feed end, taking with it high volumes of feedpowder, or if pelletized, taking the abraded powder off the pellets andmoving it to bag houses or other methods of dust capture. The discoverydisclosed in embodiments of the present invention include the effect ofthe speed of gas evolution in the first heating stages, the removal ofsaid gases, and perhaps even the impact on morphology of the finalproduct. Past technologies have shown the use of calcining temperaturesfrom about 900° C. to about 1275° C. and may have also shown theformation of enstatite and clinoenstatite when calcining. The formationof those products is not the subject of this invention, but the methodsto achieve various quality parameters in the final product is a keysubject. It is no longer necessary to accept blindly whatever productcomes out of the calciner—the products can be engineered, perhapsbeginning at the feed end.

The key quality parameters sought by firms now calcining talc, inaddition to retaining the lamellarity (platyness) of talc, are theL*a*b* values, hue, chromaticity, the surface area, specific gravity,and refractive index of the pigments produced by calcinations.

The thermal conversion of feed such as talc to products such asenstatite (between about 1100° C. to about 1220° C.) may provideproducts which are no longer talc, and may or may not have properties oftalc. For example, talc is hydrophobic, while enstatite is hydrophyllic.Depending on the conditions under which the transformation occurs,product softness or hardness, platy morphology, density, refractive andother properties may be impacted. Chemically, in addition to the above,inert siloxane bridges may be replaced by active hydrophyllic groups.X-ray diffraction patterns may demonstrate that the former talcsubstance is no longer talc.

Talc has for many years been used in the production of various ceramics,and researchers have found that heating (e.g., calcining) totemperatures in the about 1200° C. range changes the soft, platycrystals to ceramic, elongated crystals that can be sharp edged andhaving Mohs hardness in the 5 to 7 range.

The products developed using embodiments of the present invention havemany uses, including but not limited to, a partial substitution for theuse of titanium dioxide in paints, plastics, elastomers, caulks andsealants, and other products. The ceramic pigments (e.g., enstatite,clino-enstatite, or the like) produced may also be used for specialtyhigh temperature greases and lubricants, as well as exotic ceramics suchas is found in space shuttle tiles or in the proppants used in hydraulicfracturing of horizontal gas and oil wells. This may be a desirablepartial substitution because talc feed and its products may be more costeffective to utilize than the current or existing technology.

In the past, calcining may involves heating a tube or igniting naturalgas, propane, fuel oil, or other hydrocarbon materials. The mineral tobe calcined, such as talc, may be fed into the heated tube. In the past,the tube generally consisted of one heat zone, but may have a slightlycooler heat zone at the feed end due to the heat exchange which isoccurring between the cold feed, the environment, and the calciningtube. Gasses which are given off during the chemical conversion of feedto products have been pulled off with combustion gasses in such a manneras to maintain the proper heat in the tube. Feed into the calciner canbe milled, or may be of larger generally uniform size. Moreover productcan also be milled when required, but clearly the cost of milling softfeed talc is significantly less than much harder ceramic product.

Commercial use of talc and its calcined products are limited by thecolor, as assessed by the CIE L*a*b* scale, the size and sizedistribution, and other mineral specific properties. For example, ifadequate brightness (L* value of perhaps 98) is not obtained, theproduct materials may not be utilized in paints. If perhaps the a*value, which measures red/green color is >about 0.3 or generallyconsidered ‘red’ the secondary product materials may not be utilized incaulks. If perhaps the b* value, which measures blue/yellow is >about2.8 or generally considered too yellow, the secondary materials may beundesirable for use in plastics.

Therefore, commercial use of raw talc is often limited by the L*, a*and/or b* values. For example talc naturally occurs in multiple colorssuch as grey, black, green, pink and white. Black or grey talc can, uponcalcining, become white, in the range from L*=about 93 or higher,depending on calcining conditions. This may or may not be sufficientlybright to be utilized in paint. Thus, even if it may be less expensiveto use than titanium dioxide, it may likely not be available to serve asa substitute.

Past technologies may include U.S. Pat. No. 3,366,501 by Lamar, U.S.Pat. No. 5,229,094 by Clauss, FR Pat. No. 2,585,691 by Ducasse, U.S.Pat. No. 5,154,766 by Young, U.S. Pat. No. 5,371,051 by Pope, and U.S.Pat. No. 3,309,214 by Podschus, each incorporated by reference herein inits entirety.

U.S. Pat. No. 3,366,501 by Lamar may provide a method of producing awhite ceramic enstatite pigment from talc, which may be hydrophilic andcan be used for paper and paint manufacturing. The L*a*b* values are notmentioned or discussed. Lamar may utilize a direct-fired calciner andthe product may milled to a particle size d50 of 6 microns or larger toproduce a saleable powder.

U.S. Pat. No. 5,229,094 by Clauss may describe talc undergoing chemicalor thermal transformation wherein the talc particles may be heated to atemp below 900° C. perhaps under conditions to avoid conversion of talcto enstatite.

Patent FR 2,585,691 A1 by Ducasse may describe a method of preparing afine lamellar calcined talc powder perhaps in a direct-fired rotary kilnfrom a talc feed first milled to d50 of 10 microns and then milled againto d50 of 3.5 microns.

U.S. Pat. No. 5,154,766 by Young may provide raw kaolin that may beslurried with the addition of some magnetite, flocculated with aluminumand sulfuric acid, perhaps even run through a filter press to produce acake which was dried. However, the product of the Young patent may notbe acceptable as a talc-enstatite product and therefore cannot beconsidered useful.

U.S. Pat. No. 5,371,051 by Pope et. al. may attempt to increase theopacity of calcined kaolin pigments perhaps by the addition or retentionof small percentages of titanium dioxide. This method may not bepractical due to the additional cost of titanium dioxide.

U.S. Pat. No. 3,309,214 by Podschus may provide double calcinations ofkaolin, first in a shock calciner at 400° C. to 500° C. for one secondwhereby the turbulent hot gas stream may partially change the crystalstructure, and then in a second calciner of varying types for about onehour at about 800° C. to 1100° C. This process may have achieved someimprovement over competitive kaolin processes but the improvement doesnot translate to talc processing. The vertical turbulent shock calcinermay not provide sufficient residence time to be beneficial to color, orto completely calcine talc to enstatite.

In the past, controlling the production of the L*a*b* values has notbeen commercially feasible because calcination and the end products mayappear to be a somewhat random event, perhaps resulting in unpredictableproducts which may have unpredictable L*a*b* values. Moreover, mineralqualities such as platyness (or lamellarity), opacity, softness,strength, or the like may affect the commercial value and may also beconsidered somewhat uncontrolled as secondary products are produced viacalcination of minerals. By contrast, embodiments of the presentinvention addresses and demonstrates the beneficial impact ofcontrolling the calcination process and systems.

SUMMARY OF THE INVENTION

Colored talcs and secondary products produced from calcination aresalable in narrow market niches today, but with the processes andmethods as described in the various embodiments of the presentinvention, minerals and even low value talcs may be transformed intohigh value products for the talc producer, and perhaps at the same time,provide cost effective pigments and opacifiers for paint, plastics,sealer, and perhaps many other markets. Embodiments of the presentinvention may define a method for retaining the beneficial platyness ofmany talcs, while providing the benefit of opacity, high brightness,softness, and strength as well as controlling the final L*a*b* values.

Therefore, an object of the present invention may include enhancing thewhiteness characteristics of the mineral process-feed in a manner whichmight produce consistent and repeatable color values in the product asassessed by a CIE L*a*b* value, and may even provide manipulation of thevariables in the process, such as a manipulation of the color values tothose desirable for a particular end use.

Another object of the present invention may include the combination oflow-iron talc feed with progressively higher temperatures in a calciningtube of a calcinator, perhaps with specific inorganic metal oxides whichmay engineer varying a* and b* values and may create a desired platyceramic pigment at very high L* values.

Another object of the present invention may include changing the opacityof the clear talc crystals to an opaque crystal with varying degrees ofopacity, depending on the process parameters.

Another object of the present invention may include defining the processparameters, perhaps from mineral feed input temperatures to calcinerresidence, maximum temperatures, and even residence time, or the like.

Yet another object of the present invention may include defining themethod by which color parameters of secondary products, including butnot limited to enstatite products, or the like, may be manipulatedconsistently and on a production basis.

Another object of the present invention may include defining the mineralore types which can most successfully be converted to desirablesecondary products, such as enstatite or the like.

Another object of the present invention may include defining the impactof metals and metal alloys which comprise the calciner tube of therotating calciner.

Yet another object of the present invention may include defining theparameters of handling of the evolved process gases so as to preventdeleterious impacts to the final product.

Another object of the present invention may include providing aneconomical talc calcination system that avoids use of titanium dioxide.

Yet another object of the present invention may include providing a talccalcination system utilizing methods and apparatus that provide a betterproduct over past systems.

Other objects of the present invention can be found in thespecification, figures, and claims of this application.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 represents a general schematic of a talc calcination systemaccording to the various embodiments of the present invention.

FIG. 2 represents an alternate talc calcination system according to thevarious embodiments of the present invention which may provide greatercontrol of the temperature in perhaps a first and second zone of acalciner perhaps by reducing heat carry-over from a third zone.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention includes a variety of aspects, which may becombined in different ways. The following descriptions are provided tolist elements and describe some of the embodiments of the presentinvention. These elements are listed with initial embodiments, howeverit should be understood that they may be combined in any manner and inany number to create additional embodiments. The variously describedexamples and preferred embodiments should not be construed to limit thepresent invention to only the explicitly described systems, techniques,and applications. Further, this description should be understood tosupport and encompass descriptions and claims of all the variousembodiments, systems, techniques, methods, devices, and applicationswith any number of the disclosed elements, with each element alone, andalso with any and all various permutations and combinations of allelements in this or any subsequent application

In general, the present invention may include systems and methods forcalcination of minerals including creation of desired end products to beutilized in unique applications. In embodiments, various techniques forutilizing minerals from various sources may easily be exemplified bytalc, kaolin, zinc oxide, barium sulfate or others.

The present invention may provide talc calcination systems (50) andmethods for talc calcination. Calcination may involve providingmaterials (13) for introduction into a calciner. Materials (13) mayinclude but are not limited to, minerals, talc, low iron talc,combinations thereof, or the like. Minerals may include but are notlimited to talc, kaolin, zinc oxide, barium sulfate, pyrophyllite,calcium carbonate, diatomite, mica, any combinations thereof, or thelike. Low iron talc may include but is not limited to talc having lessthan about 1.0% iron by weight; less than about 0.5% iron by weight;between about 0.4% to about 0.01% iron by weight; less than about 0.4%iron by weight; less than about 0.01% iron by weight, or the like. Ironmay be Fe₂O₃ or other iron compounds. Materials may include an amount ofcarbonates therein including but not limited to about 10% carbonates byweight; less than about 20% carbonates by weight; less than about 15%carbonates by weight; less than about 10% carbonates by weight; betweenabout 10% and about 15% carbonates by weight; between about 5% and about10% carbonates by weight, or the like.

Materials (13), such as low iron talc, may be milled to provide a milledcomposition, or may include coloration prior to being fed into a hopper(8, 9) which may be a pre-blend bin or the like. Milled materials mayinclude but is not limited to a median particle size selected from agroup consisting of less than about 7 microns; less than about 3microns, less than about 1 micron, or the like. In addition, milledmaterials may have a size up to about 20 microns. In some embodiments,materials or even milled materials may be mixed with at least one metaloxide (14) perhaps with a mixer (10). In other embodiments, materials,such as low iron talc, may not be mixed with at least one metal oxide.Examples of a mixer may include but is not limited to a powder blender,ribbon blender, a pug-mill blender, other blenders commerciallyavailable for powder mixing, so as to achieve a violent and thoroughblend, prior to introduction into the calciner. or the like. The mixturemay be moved to a feed bin perhaps by a conveyor (11) or the like. Afeed supply (1) which may include a milled composition of minerals, lowiron talc, a combination thereof or the like that may be mixed with atleast one metal oxide may be augured or otherwise fed (2) into acalciner (3). A feed input controller (16) may control the rate at whicha feed is introduced into a calciner and may even control the rate atwhich the feed is processed in the calciner. The feed may moves throughthe calciner (3) for processing perhaps at a specified rate for the feedand product specifications. Gasses (7) that may be given off duringcalcining may be removed with a gas removal system. A gas removal systemmay remove gas at a controlled rate. Off-gassing rates may affect aproduct (4) output quality.

A product may include a composition including but not limited toenstatite; proto-enstatite; clino-enstatite; diopside; at least about25% enstatite; up to about 44% enstatite; at least about 20% ofclino-enstatite; up to about 42% of clino-enstatite; between about 12%and about 37% of diopside; any combination thereof, or the like.

In embodiments, the present invention may provide a calciner (3) whichmay be an indirectly heated, multiple zone calciner, may even be arotating calciner. Zones of a calciner may include any continuous tractor area that differs in some respect, or is distinguished for somepurpose, or may have certain distinctive characteristics. As may beunderstood from FIG. 1, zones may include a first heat zone (20), asecond heat zone (21), and a third heat zone. In some embodiments, aheat zone (25) may be considered a third heat zone, which may be acombination of at least two sub zones, at least three sub heat zones, orthe like to create a third heat zone. In other embodiments a heat zone(22) may be considered a third heat zone. At least one additional heatzone may be provided in a calciner perhaps as a fourth zone (23) or afifth zone (24), in some embodiments. Of course, any number of zones maybe provided in a calciner including but not limited to at least twozones, at least three zones, at least four zones, at least five zones,at least six zones, or more or the like and all are meant to be includedin the disclosure of this invention. In some embodiments, at least oneadditional heat zone may have a substantially same temperature as thethird heat zone. Alternatively, at least one additional heat zone mayhave different temperatures. A cooling zone (26) may be provided to coolthe product prior to output of the product (4). In embodiments, acooling zone may cool a product to about 150° C. The temperature of afinal cooling zone may be unheated and take the blended temperature of afinal heated zone and ambient temperature to bring the temperature ofthe product to about 150° C. perhaps to enable handling of the productoutput such as in a product-off-take system.

In embodiments, a calciner (3) may be divided into differentially heatedzones, each zone heated indirectly and perhaps even progressively. Thezones may be variably heated in that one zone could be heated to adifferent temperature than another zone or that each zone temperaturecan be controlled separately perhaps with at least one indirect heatsource (6). An indirect heat source may be controlled by a temperaturecontroller (17). In embodiments, each zone may be heated by more thanone indirect heat sources (6) as may be understood from FIG. 1. Anindirect heat source may be located outside of the calciner. A firstheat zone may be considered a CO₂ evolution zone where CO₂ may evolvefrom the feed supply. A first heat zone may have a temperatureincluding, but not limited to, between about 500° C. and about 875° C.;between about 550° C. and about 850° C.; between about 575° C. and about800° C.; about 850° C., or the like. A second heat zone may beconsidered a H₂O evaluation zone where H₂O may evolve from the feedsupply. A second heat zone may have a temperature including, but notlimited to, between about 750° C. and about 1000° C.; between about 750°C. and about 1100° C.; between about 775° C. and about 1050° C.; betweenabout 800° C. and about 1000° C.; about 1000° C., or the like. A thirdheat zone may be considered a hot zone having a temperature includingbut not limited to, between about 1100° C. and about 1200° C.; betweenabout 1100° C. and about 1125° C.; between about 1100° C. and about1150° C.; between about 1100° C. and about 1175° C.; between about 1125°C. and about 1150° C.; between about 1125° C. and about 1200° C.;between about 1150° C. and about 1200° C., about 1125° C., about 1150°C., about 1175° C., or the like. In embodiments, a feed supply may beprocessed in a first zone for an amount of time including but notlimited to about 5 minutes; between about 3 and about 10 minutes;between about 5 and about 10 minutes, or the like. A feed supply may beprocessed in a second zone for an amount of time including but notlimited to, about 5 minutes; between about 3 and about 10 minutes;between about 5 and about 10 minutes, or the like. A feed supply may beprocessed in a third zone for an amount of time including but notlimited to about 5 minutes, about 10 minutes, about 15 minutes, about 20minutes, about 30 minutes, about 40 minutes, about 50 minutes, betweenabout 10 and about 30 minutes; between about 15 minutes and about 18minutes; between about 18 minutes and about 22 minutes; between about 5minutes and about 50 minutes, or the like.

When the product is outputted from the calciner, it may have desirablecharacteristics such as but not limited to color and physicalcharacteristics perhaps for final use in materials such as plastics,paint, paper, and the like.

In embodiments, a calciner tube (15) may include at least one alloywhich may allow an increase in temperature of the calciner perhapsbeyond that which can be achieved in a traditional iron calcining tube.For example, an alloy may include but is not limited to nickel,chromium, a combination to the two, or the like. Alloys may allow thecalciner to achieve up to about 1225° C. inside the calciner. A calcinertube may be a sufficient length to maintain differential temperaturezones.

The present invention may provide in embodiments, the use of metaloxides such as metal oxide stains or other stains or the like. Metaloxides, stains, or the like may proactively counteract residual feed orproduct hue, or the like. Non limiting examples of stains include butare not limited to any stains that can achieve shifting of a* and b*values, Mason 6374; Mason 6376; Mason 6315; Mason 6242; Mason 6206;Mason 6263; Mason 6364; any combination thereof, any stains utilized forshifting the a* and b*value toward negative values; similar compositionsand brands, or the like. An amount of stain may vary based on thespecific system characteristics. A non-limiting example of amount ofstains include, but is not limited to, between about 0.5% and about0.75% of the total feed by weight; between about 0.25% and about 0.5% ofthe total feed by weight; between about 0.10% and about 0.25% of thetotal feed by weight; between about 0.01% and about 0.10% of the totalfeed by weight, or the like. The feed supply (1) to be calcined mayinclude a stain perhaps to affect a coloration change in the finalproduct. Metal oxides or stains can be added to the feed or may even beadded to the output product or both. When, included in the feed supply,the final L*a*b* values of the product output may be influenced. Someproducts may have L* values between about 95 and about 99.9. Theadditions may be selected based on a desired effect, can be influencedby the type of feed, the amount of stain blended with the materials, thetemperature of calcining, the residence time, or the like. The varianceof temperature effectiveness may be about 25° C. more or less.Therefore, specific testing may be required prior to stain selection.The type of particular stain may have particular chemical elements andcompounds which may influence the shift of the L* a* and b* values. Aparticular problem of a paint, plastic, or other producers can beresolved by the addition of particular metal oxides to feed perhaps tocounteract such producer's problems with, for example, a particularpolypropylene which may have yellowish hues or the like. The amount andtype of colorant may be adjusted in the feed perhaps in anticipation ofthe degree of yellowness expected, perhaps removing a problem in the endproduct, and even reducing expenses of plastic production.

In an alternative embodiment, a calciner (40) may be an isolatedcalciner as may be understood in FIG. 2. A calciner (40) may be a singleconnected tube or may even be a multiple-pieced zones perhaps as atleast two separate pieces or even three separate pieces (43, 42, and 41)as a non-limiting example. Of course any number of pieces may be used. Acalciner may have at least two isolated zones, at least three isolatedzones or more or the like. A seal (12) may be used between each zone.Accordingly, as may be understood from FIG. 2, a feed input (30) may beintroduced into a first zone (31) of a calciner (40) for processing at afirst temperature in the first zone perhaps with heat supplied by aseparate heating source (6). Then, the feed may move (37) into a secondzone (32) for processing at a second temperature perhaps with heatsupplied by a separate heating source (6). Then, the feed may move (38)into a third zone (33) for processing at a second temperature perhapswith heat supplied by at least one separate heating source (6). Thethird zone may include multiple zones. Alternatively, the feed may beprocessed in a third zone (33), a fourth zone (34), and perhaps even afifth zone (35). A product may then be cooled in a cooling zone (36) andmay be exited from the calciner as a product output (39).

As mentioned herein, embodiments of the present invention may include agas removal system (5). A rate of off-gassing, and even residence time,and perhaps calciner tube composition and other parameters may affectcolor as well. The capacity of the gas removal system may account forthe expansion of air entrained in the feed talc. In embodiments, adesired product output may be determined. From this determination a feedrequirement and size of the gas removal system may be calculated inorder to provide a system that can remove all of the evolved gases froman amount of feed. Therefore, in some embodiments, a feed inputcontroller may be configured to control the rate of feed input tocontrol a rate of off-gassing in said calciner. A rate of feed inputinto said first heat zone may be designed to match a capacity of theoff-gas system to remove all evolved gas. Evolved gases (7) may includebut is not limited to carbon dioxide, water vapor, entrained air, anycombination thereof, or the like.

Surface area testing clarifies that the stain or colorant is adsorbedonto the lattice or crystal structure of the end product in a sinteringprocess and can help reduce the surface area of the product particles,significantly reducing the oil absorptive capacity of the product. Thus,as a result of embodiments of the present invention, a product may haveless surface area perhaps because the crystal may shrink and may resultin a reduced oil capacity. In embodiments, the surface area of a productmay include but is not limited to about 12 m²/gm; about 4 m²/gm; about 3m²/gm; about 2 m²/gm; any combination thereof, or the like.

The present invention provides, in embodiments, a combination ofparameters which when implemented, may consistently produce a specificproduct for a specific industry. Specifically, as a non-limitingexample, when a process temperature may be within a range of +/−10° C.,a feed rate may match the ability of the calciner to remove evolvedgases, the colorants are within the desired weight percent range, andperhaps even the mineral feed has nearly the same properties, theresulting product can have L*a*b* values that are substantiallyidentical (e.g., the lamellarity can be similar, and properties such asdensity, surface area, refractive index can be substantially the same).Thus, the process is repeatable and predictable.

As mentioned herein, a calciner may have various zones that may havedifferent temperatures. In embodiments, the temperature may be raised asthe feed supply may move from one zone to another. By raising thecalcining temperature in stages, evolved gases may be removedappropriately, perhaps with a time and temperature relationship in eachzone, until a final temperature is achieved. Results have showndramatically different product results when altering individual, singleparameters perhaps via each zone. For example, when talc is introducedinto a calciner heated to 1100° C., a violent evolution of carbondioxide, water and entrained air may occur, resulting in the formationof shards from the formerly platy material, cancelling one significantbenefit of talc. Likewise, if evolved gases are not removed from thecalciner as quickly as evolved, and perhaps if they exert a slightpressure increase, the L*a*b* color values may be negatively impacted.For example, the L* values may be depressed, a* values may have atendency toward red, and b* values may have a tendency toward yellow.The chromaticity (saturation) may also have a tendency toward lowervalues. Embodiments of the present invention have also determined thatthe refractive index of the products could be altered, depending on thespecific temperature applied in the process.

As mentioned herein, the present invention provides, in embodiments,indirect heating of a calciner. Indirect heating such as indirect firingmay keep combustion gases away from the product and may result in aproduct which has no hydrocarbon contamination—thus may provide acleaner product. Indirect heating may reduce product loss up to about90% or more perhaps due to combustion gas movement to the vent stacks.Indirect heating may reduce energy cost by up to about 30% or moreperhaps by keeping the heat contained within the calciner. Indirectheating may not require a ceramic or fire-brick lining and may evenallow feed to be in contact with calciner tube alloys which may have abeneficial impact on product quality. Indirect firing may allow use ofextremely fine feed powders, even to sub-micron sizes in the system.Indirect firing may not wet or pelletize the feed, perhaps removing therequirement for post-calcining milling and even the resultant productlosses and lowering production costs.

In embodiments, it was determined that it may not be necessary to have aceramic or even fire-brick lined calciner tube, and in fact, thepresence or absence of various metals in the calciner tube which came incontact with the feed talc, may have beneficial or even detrimentalimpacts on the product properties, as compared to the values achievedusing ceramic labware and equipment. Specifically the presence ofcalciner tube alloys containing nickel and chromium appeared beneficialin achieved desirable L*a*b* values. In embodiments, at least one alloymay be present in a calciner tube, including but not limited to nickel;chromium; at least about 11% nickel; up to about 35% nickel; up to about52% nickel; at least about 18% chromium; up to about 25% chromium; up toabout 35% chromium; any combination thereof; or the like. Thus, inspecifying alloy materials of the indirect fired calciner, thecomposition of the desired alloys should be considered in addition tothe heating properties normally considered when purchasing a hightemperature calciner.

In some embodiments, a feed supply or even a product resulting from acalcination system may be treated perhaps with a product outputtreatment (18) or the like. For example, a treatment may include but isnot limited to a brightness treatment, a hydrophillicity enhancementtreatment; a hydrophillicity reduction treatment; a light reflectanceenhancement treatment; inorganic surface treatment, organic surfacetreatment; any combination thereof, or the like. A treatment may includean additive such as but not limited to alumina, zirconia, titaniumdioxide, and any combination thereof. Additives may be blended with aproduct after processing; however some additives may be added to thefeed. Alumina, for example, may not be added to the feed because it maymelt and evaporate, but finely milled alumina could be blended with theceramic pigment product in commercially available blenders. Accordingly,a product may accept and hold inorganic or even organic surfacetreatments and/or additives such as alumina, zirconia, titanium dioxide,or similar treatments, applied according to commonly known methods orprocedures.

EXAMPLES

In Table 1, it can be seen that increasing calcining temperatures, up tothe melting point of talc, can increase the refractive index,benefitting users of paints and plastics who desire greater hue andsaturation. Talc (starting material 600 D) is heated to three differenttemperatures producing an increased specific gravity, a decreasedsurface area and BET which decreases significantly between 800° C.,1150° C., and 1225° C.

In Table 2, it can be seen that the specific gravity is increased withincreasing temperature, thus allowing a plastics producer to increasehis production rate if more pigment product is contained in hisextrusion equipment, thus reducing his cost. It may also help reducetransportation costs when a denser product can be hauled in trucks, forexample.

Additionally in Table 2, it can be seen that surface area of productcrystals decreases due to sintering as the product approaches themelting point in the calciner, when the surface of the crystals becomesflatter, filling in the ‘valleys’ on the crystal surface. Sintering is aprocess whereby powders are held to a temperature just below the meltingpoint, allowing the atoms in the powder particles to diffuse acrossparticle boundaries, thus fusing particles or surfaces together. Thisreduction in surface area is particularly helpful for a paintmanufacturer who can then reduce his oil usage cost by using atalc-derived pigment which absorbs less oil.

Table 2 summarizes the effects of high temperature and several differentoxide treatments on the CIE L*a*b* values to demonstrate how the processcan be controlled to produce desired product results. To compare thevalues of the newly produced pigments with commercially availabletitanium dioxide pigments, the L*a*b* values of RD3 titanium dioxide(TiO₂) and TRONOX CR-828(TiO₂) are shown.

Table 3 shows the solar reflectance and thermal emittance of titaniumdioxide, and ceramic pigments with titanium dioxide.

TABLE 1 Surface Area m² per gram Specific Gravity Product Single PointBET grams per cc 600D - raw talc 9.3685 9.4867 2.8023 At 800° C. 8.50278.7497 2.8571 At 1150° C. 6.8631 7.0563 2.9859 At1225° C. 0.5340 0.55443.0490

TABLE 2 Product L* a* b* 600D-raw talc 61.72 −0.14 0.48 Test 1 99.89−0.09 2.48 Test 2 98.81 −0.47 1.21 Test 3 99.73 −0.09 1.60 Test 4 99.650.06 1.77 Test 5 98.53 −0.09 1.49 Test 6 98.73 −0.41 1.27 Test 7 99.440.04 1.62 Test 8 99.02 −0.29 1.45 RD3 TiO₂ 98.86 −0.46 2.41 TRONOXCR-828 TiO₂ 99.40 −0.55 2.35

TABLE 3 Solar Reflectance Thermal Emittance Titanium dioxide 0.85 0.9125% Ceramic Pigment 0.84 0.92 with TiO₂ 50% Ceramic Pigment 0.83 0.91with TiO₂

As can be easily understood from the foregoing, the basic concepts ofthe present invention may be embodied in a variety of ways. It involvesboth techniques as well as devices to accomplish the predictable changeof mineral feed to product possessing physical characteristics whichmake it commercially useful and feasible as a substitute for moreexpensive ingredients. In this application, the techniques forcalcining, treating mineral feed and coloring are disclosed as part ofthe results shown to be achieved by the various devices described and assteps which are inherent to utilization. They are simply the naturalresult of utilizing the devices as intended and described. In addition,while some devices, mineral, metal and colorant types are disclosed, itshould be understood that these not only accomplish certain methods butalso can be varied in a number of ways. Importantly, as to all of theforegoing, all of these facets should be understood to be encompassed bythis disclosure.

The discussion included in this application is intended to serve as abasic description. The reader should be aware that the specificdiscussion may not explicitly describe all embodiments possible; manyalternatives are implicit. It also may not fully explain the genericnature of the invention and may not explicitly show how each feature orelement can actually be representative of a broader function or of agreat variety of alternative or equivalent elements. Again, these areimplicitly included in this disclosure. Where the invention is describedin device-oriented terminology, each element of the device implicitlyperforms a function. Apparatus claims may not only be included for thedevice described, but also method or process claims may be included toaddress the functions the invention and each element performs. Neitherthe description nor the terminology is intended to limit the scope ofthe claims that will be included in any subsequent patent application.

It should also be understood that a variety of changes may be madewithout departing from the essence of the invention. Such changes arealso implicitly included in the description. They still fall within thescope of this invention. A broad disclosure encompassing both theexplicit embodiment(s) shown, the great variety of implicit alternativeembodiments, and the broad methods or processes and the like areencompassed by this disclosure and may be relied upon when drafting theclaims for any subsequent patent application. It should be understoodthat such language changes and broader or more detailed claiming may beaccomplished at a later date (such as by any required deadline) or inthe event the applicant subsequently seeks a patent filing based on thisfiling. With this understanding, the reader should be aware that thisdisclosure is to be understood to support any subsequently filed patentapplication that may seek examination of as broad a base of claims asdeemed within the applicant's right and may be designed to yield apatent covering numerous aspects of the invention both independently andas an overall system.

Further, each of the various elements of the invention and claims mayalso be achieved in a variety of manners. Additionally, when used orimplied, an element is to be understood as encompassing individual aswell as plural structures that may or may not be physically connected.This disclosure should be understood to encompass each such variation,be it a variation of an embodiment of any apparatus embodiment, a methodor process embodiment, or even merely a variation of any element ofthese. Particularly, it should be understood that as the disclosurerelates to elements of the invention, the words for each element may beexpressed by equivalent apparatus terms or method terms—even if only thefunction or result is the same. Such equivalent, broader, or even moregeneric terms should be considered to be encompassed in the descriptionof each element or action. Such terms can be substituted where desiredto make explicit the implicitly broad coverage to which this inventionis entitled. As but one example, it should be understood that allactions may be expressed as a means for taking that action or as anelement which causes that action. Similarly, each physical elementdisclosed should be understood to encompass a disclosure of the actionwhich that physical element facilitates. Regarding this last aspect, asbut one example, the disclosure of a “obtaining an appropriate mineralfeed” should be understood to encompass disclosure of the act of“obtaining”—whether explicitly discussed or not—and, conversely, werethere effectively disclosure of the act of “creating”, such a disclosureshould be understood to encompass disclosure of a “methods for making”and even a “means for creating” Such changes and alternative terms areto be understood to be explicitly included in the description.

Any patents, publications, or other references mentioned in thisapplication for patent are hereby incorporated by reference. Anypriority case(s) claimed by this application is hereby appended andhereby incorporated by reference. In addition, as to each term used itshould be understood that unless its utilization in this application isinconsistent with a broadly supporting interpretation, common dictionarydefinitions should be understood as incorporated for each term and alldefinitions, alternative terms, and synonyms such as contained in theRandom House Webster's Unabridged Dictionary, second edition are herebyincorporated by reference. Finally, all references listed theinformation disclosure statement or other information statement filedwith the application are hereby appended and hereby incorporated byreference, however, as to each of the above, to the extent that suchinformation or statements incorporated by reference might be consideredinconsistent with the patenting of this/these invention(s) suchstatements are expressly not to be considered as made by theapplicant(s).

Thus, the applicant(s) should be understood to have support to claim andmake a statement of invention to at least: i) a method and device formodifying physical components of minerals as well as methods forcalcining, ii) the related methods disclosed and described, iii)similar, equivalent, and even implicit variations of each of thesedevices and methods, iv) those alternative designs which accomplish eachof the functions shown as are disclosed and described, v) thosealternative designs and methods which accomplish each of the functionsshown as are implicit to accomplish that which is disclosed anddescribed, vi) each feature, component, and step shown as separate andindependent inventions, vii) the applications enhanced by the varioussystems or components disclosed, viii) the resulting products producedby such systems or components, ix) each system, method, and elementshown or described as now applied to any specific field or devicesmentioned, x) methods and apparatuses substantially as describedhereinbefore and with reference to any of the accompanying examples, xi)the various combinations and permutations of each of the elementsdisclosed, xii) each potentially dependent claim or concept as adependency on each and every one of the independent claims or conceptspresented, and xiii) all inventions described herein.

With regard to claims whether now or later presented for examination, itshould be understood that for practical reasons and so as to avoid greatexpansion of the examination burden, the applicant may at any timepresent only initial claims or perhaps only initial claims with onlyinitial dependencies. The office and any third persons interested inpotential scope of this or subsequent applications should understandthat broader claims may be presented at a later date in this case, in acase claiming the benefit of this case, or in any continuation in spiteof any preliminary amendments, other amendments, claim language, orarguments presented, thus throughout the pendency of any case there isno intention to disclaim or surrender any potential subject matter. Itshould be understood that if or when broader claims are presented, suchmay require that any relevant prior art that may have been considered atany prior time may need to be re-visited since it is possible that tothe extent any amendments, claim language, or arguments presented inthis or any subsequent application are considered as made to avoid suchprior art, such reasons may be eliminated by later presented claims orthe like. Both the examiner and any person otherwise interested inexisting or later potential coverage, or considering if there has at anytime been any possibility of an indication of disclaimer or surrender ofpotential coverage, should be aware that no such surrender or disclaimeris ever intended or ever exists in this or any subsequent application.Limitations such as arose in Hakim v. Cannon Avent Group, PLC, 479 F.3d1313 (Fed. Cir 2007), or the like are expressly not intended in this orany subsequent related matter. In addition, support should be understoodto exist to the degree required under new matter laws—including but notlimited to European Patent Convention Article 123(2) and United StatesPatent Law 35 USC 132 or other such laws—to permit the addition of anyof the various dependencies or other elements presented under oneindependent claim or concept as dependencies or elements under any otherindependent claim or concept. In drafting any claims at any time whetherin this application or in any subsequent application, it should also beunderstood that the applicant has intended to capture as full and broada scope of coverage as legally available. To the extent thatinsubstantial substitutes are made, to the extent that the applicant didnot in fact draft any claim so as to literally encompass any particularembodiment, and to the extent otherwise applicable, the applicant shouldnot be understood to have in any way intended to or actuallyrelinquished such coverage as the applicant simply may not have beenable to anticipate all eventualities; one skilled in the art, should notbe reasonably expected to have drafted a claim that would have literallyencompassed such alternative embodiments.

Further, if or when used, the use of the transitional phrase“comprising” is used to maintain the “open-end” claims herein, accordingto traditional claim interpretation. Thus, unless the context requiresotherwise, it should be understood that the term “comprise” orvariations such as “comprises” or “comprising”, are intended to implythe inclusion of a stated element or step or group of elements or stepsbut not the exclusion of any other element or step or group of elementsor steps. Such terms should be interpreted in their most expansive formso as to afford the applicant the broadest coverage legally permissible.The use of the phrase, “or any other claim” is used to provide supportfor any claim to be dependent on any other claim, such as anotherdependent claim, another independent claim, a previously listed claim, asubsequently listed claim, and the like. As one clarifying example, if aclaim were dependent “on claim 20 or any other claim” or the like, itcould be re-drafted as dependent on claim 1, claim 15, or even claim 715(if such were to exist) if desired and still fall with the disclosure.It should be understood that this phrase also provides support for anycombination of elements in the claims and even incorporates any desiredproper antecedent basis for certain claim combinations such as withcombinations of method, apparatus, process, and the like claims.

Finally, any claims set forth at any time are hereby incorporated byreference as part of this description of the invention, and theapplicant expressly reserves the right to use all of or a portion ofsuch incorporated content of such claims as additional description tosupport any of or all of the claims or any element or component thereof,and the applicant further expressly reserves the right to move anyportion of or all of the incorporated content of such claims or anyelement or component thereof from the description into the claims orvice-versa as necessary to define the matter for which protection issought by this application or by any subsequent continuation, division,or continuation-in-part application thereof, or to obtain any benefitof, reduction in fees pursuant to, or to comply with the patent laws,rules, or regulations of any country or treaty, and such contentincorporated by reference shall survive during the entire pendency ofthis application including any subsequent continuation, division, orcontinuation-in-part application thereof or any reissue or extensionthereon.

1-92. (canceled)
 93. A method of talc calcination comprising the stepsof: milling low iron talc to provide a feed supply; inputting said feedsupply into a multiple zoned calciner comprising a calciner tube havingat least one alloy; externally heating said multiple zoned calciner;heating said feed supply via heat exchange between said heated calincerand said feed supply in at least three zones of said multiple zonedcalciner; processing said feed supply in said at least three zones ofsaid multiple zoned calciner resulting in a product; cooling saidproduct; and outputting said product.
 94. A method of talc calcinationaccording to claim 93 wherein said low iron talc is selected from agroup consisting of: less than about 1.0% iron by weight; less thanabout 0.5% iron by weight; between about 0.4% to about 0.01% iron byweight; less than about 0.4% iron by weight; and less than about 0.01%iron by weight.
 95. A method of talc calcination according to claim 93wherein said milled composition comprises an amount of carbonatesselected from a group consisting of: about 10% carbonates by weight;less than about 20% carbonates by weight; less than about 15% carbonatesby weight; less than about 10% carbonates by weight; between about 10%and about 15% carbonates by weight; between about 5% and about 10%carbonates by weight; and between about 5% and about 20% carbonates byweight.
 96. A method of talc calcination according to claim 93 whereinsaid iron comprises Fe₂O₃.
 97. A method of talc calcination according toclaim 93 wherein said product comprises a composition selected from agroup consisting of enstatite; proto-enstatite; clino-enstatite;diopside; at least about 25% enstatite; up to about 44% enstatite; atleast about 20% of clino-enstatite; up to about 42% of clino-enstatite;between about 12% and about 37% of diopside; and any combinationthereof.
 98. A method of talc calcination according to claim 93 whereinsaid step of processing said feed supply in said at least three zones ofsaid multiple zoned calciner resulting in said product comprises thestep of producing a product having an L* value between about 95 andabout 99.9.
 99. A method of talc calcination according to claim 93wherein said step of processing said feed supply in said at least threezones of said multiple zoned calciner comprises the step of evolving CO₂from said feed supply in a first zone of said multiple zoned calciner.100. A method of talc calcination according to claim 93 wherein saidstep of processing said feed supply in said at least three zones of saidmultiple zoned calciner comprises the step of processing said feedsupply in a first zone comprises a temperature selected from a groupconsisting of between about 500° C. and about 875° C.; between about550° C. and about 850° C.; between about 575° C. and about 800° C.; andabout 850° C.
 101. A method of talc calcination according to claim 93wherein said step of processing said feed supply in said at least threezones of said multiple zoned calciner comprises the step of evolving andremoving H₂O, vapor, and entrained air from said feed supply in a secondzone of said multiple zoned calciner.
 102. A method of talc calcinationaccording to claim 93 wherein said step of processing said feed supplyin said at least three zones of said multiple zoned calciner comprisesthe step of processing said feed supply in a second zone comprising atemperature selected from a group consisting of: between about 750° C.and about 1000° C.; between about 750° C. and about 1100° C.; betweenabout 775° C. and about 1050° C.; between about 800° C. and about 1000°C.; about 1000° C., and about 1050° C.
 103. A method of talc calcinationaccording to claim 93 wherein said step of processing said feed supplyin said at least three zones of said multiple zoned calciner comprisesthe step of processing said feed supply in a third hot zone of saidmultiple zoned calciner.
 104. A method of talc calcination according toclaim 103 wherein said step of processing said feed supply in said atleast three zones of said multiple zoned calciner comprises the step ofheating said feed supply in a third hot to a temperature selected from agroup consisting of: between about 1100° C. and about 1200° C.; betweenabout 1100° C. and about 1125° C.; between about 1100° C. and about1150° C.; between about 1100° C. and about 1175° C.; between about 1125°C. and about 1150° C.; between about 1125° C. and about 1200° C.; andbetween about 1150° C. and about 1200° C.
 105. A method of talccalcination according to claim 103 wherein said third hot zone comprisesa temperature selected from a group consisting of about 1125° C., about1150° C., about 1175° C., about 1200° C. and about 1225° C.
 106. Amethod of talc calcination according to claim 103 wherein said step ofprocessing said feed supply in said at third hot zone comprises the stepof processing said feed supply in said third zone for an amount of timeselected from a group consisting of: about 5 minutes, about 10 minutes,about 15 minutes, about 20 minutes, about 30 minutes, about 40 minutes,about 50 minutes, between about 10 and about 30 minutes; between about15 minutes and about 18 minutes; between about 18 minutes and about 22minutes; and between about 5 minutes and about 50 minutes.
 107. A methodof talc calcination according to claim 93 wherein said step ofprocessing said feed supply in said at least three zones comprises thestep of processing said feed supply in a first zone and separately in asecond zone for an amount of time selected from a group consisting of:about 5 minutes; between about 3 and about 10 minutes; and between about5 and about 10 minutes.
 108. A method of talc calcination according toclaim 103 wherein said third hot zone comprise sub hot zones selectedfrom a group consisting of: at least two sub hot zones; at least threesub hot zones, three hot zones, and more than three hot zones.
 109. Amethod of talc calcination according to claim 93 wherein said step ofcooling said product comprises the step of cooling said product to about150° C.
 110. A method of talc calcination according to claim 93 whereinsaid step of processing said feed supply in said at least three zones ofsaid multiple zoned calciner comprises the step of controlling a rate ofgas removal of evolved gas in said multiple zoned calciner.
 111. Amethod of talc calcination according to claim 93 wherein said step ofmilling said minerals and said low iron talc comprises the step ofmilling said minerals and said low iron talc to a median particle sizeselected from a group consisting of up to about 20 microns, less thanabout 7 microns; less than about 3 microns, and less than about 1micron.
 112. A method of talc calcination according to claim 93 andfurther comprising the step of mixing said milled low iron talc with atleast one metal oxide stain to provide said feed supply.
 113. A methodof talc calcination according to claim 112 and further comprising thestep of adding an amount of said at least one metal oxide to saidminerals based on a desired a* or b* value.
 114. A method of talccalcination according to claim 112 wherein said metal oxide staincomprises a stain configured to shift an a* or b* value of a productoutput.
 115. A method of talc calcination according to claim 112 whereinsaid metal oxide stain comprises an amount of metal oxide stain of thetotal mineral mixture by weight selected from a group consisting of:between about 0.5% and about 0.75% of the total mineral mixture byweight; between about 0.25% and about 0.5% of the total mineral mixtureby weight; between about 0.10% and about 0.25% of the total mineralmixture by weight; and between about 0.01% and about 0.10% of the totalmineral mixture by weight.
 116. A method of talc calcination accordingto claim 93 wherein said step of externally heating said multiple zonedcalciner comprises the step of progressively heating each of said atleast three zones of said calciner.
 117. A method of talc calcinationaccording to claim 93 wherein said step of indirect variably heatingsaid at least three zones of said multiple zoned calciner comprises thestep of indirect variably heating said at least three zones with anexternal heat source.
 118. A method of talc calcination according toclaim 93 wherein said calciner tube of said calciner comprises a singleconnected tube.
 119. A method of talc calcination according to claim 93wherein said calciner tube of said calciner comprises at least twoseparate pieces.
 120. A method of talc calcination according to claim 93wherein said step of mixing said minerals and said low iron talc withsaid at least one metal oxide comprises the step of mixing withcommercially available blenders.
 121. A method of talc calcinationaccording to claim 93 wherein said product comprises a surface areaselected from a group consisting of about 12 m²/gm; about 4 m²/gm; about3 m²/gm; about 2 m²/gm; or any combination thereof.
 122. A method oftalc calcination according to claim 93 wherein said at least one alloyof said calciner tube is selected from a group consisting of nickel;chromium; at least about 11% nickel; up to about 35% nickel; up to about52% nickel; at least about 18% chromium; up to about 25% chromium; up toabout 35% chromium; and any combination thereof.
 123. A method of talccalcination according to claim 93 and further comprising the step oftreating said feed supply or said product.
 124. A method of talccalcination according to claim 123 wherein said step of treating saidfeed supply or said product comprises the step of treating said feedsupply or product with a treatment selected from a group consisting of abrightness treatment, a hydrophillicity enhancement treatment; ahydrophillicity reduction treatment; a light reflectance enhancementtreatment; inorganic surface treatment, organic surface treatment; andany combination thereof.
 125. A method of talc calcination according toclaim 93 wherein said step of inputting said feed supply into saidmultiple zoned calciner comprises the step of inputting said feed supplyby a conveyer into said multiple zoned calciner.
 126. A method of talccalcination according to claim 93 wherein said multiple zoned calcinercomprises a multiple zoned rotating calciner.